A Ni3O-cluster based porous MOF for catalytic conversion of CO2 to cyclic carbonates

Article abstract of DOI:10.1016/j.jssc.2019.05.010

A novel Ni₃O-based MOF, {[Ni₃HL(μ₃-OH)(H₂O)₂]?3(H₂O)?DMA}_n (1), was constructed based on an organosilicon hexacarboxylic acid linker of 5,5′,5''-(methylsilanetriyl)triisophthalic

Full text of DOI:10.1016/j.jssc.2019.05.010

Accepted Manuscript
A Ni O-cluster based porous MOF for catalytic conversion of CO to cyclic
3
2
carbonates
Yang Yang, Zhenli Guo, Xiao-Hong Chen, Jinglin Liu
PII:
S0022-4596(19)30235-X
https://doi.org/10.1016/j.jssc.2019.05.010
YJSSC 20753
DOI:
Reference:
To appear in: Journal of Solid State Chemistry
Received Date: 26 March 2019
Revised Date: 7 May 2019
Accepted Date: 8 May 2019
Please cite this article as: Y. Yang, Z. Guo, X.-H. Chen, J. Liu, A Ni O-cluster based porous MOF for
3
catalytic conversion of CO to cyclic carbonates, Journal of Solid State Chemistry (2019), doi: https://
2
doi.org/10.1016/j.jssc.2019.05.010.
This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to
our customers we are providing this early version of the manuscript. The manuscript will undergo
copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please
note that during the production process errors may be discovered which could affect the content, and all
legal disclaimers that apply to the journal pertain.

ACCEPTED MANUSCRIPT

ACCEPTED MANUSCRIPT
A Ni3O-cluster based porous MOF for catalytic conversion of
CO2 to cyclic carbonates
Yang Yang,* Zhenli Guo, Xiao-Hong Chen, Jinglin Liu
Inner Mongolia Key Lab of Carbon Nanomaterials, Nano Innovation Institute (NII),
College of Chemistry and Chemical Engineering, Inner Mongolia University for the
Nationalities (IMUN), Tongliao 028000, People’s Republic of China.
E-mail addresses: yangyang-000@163.com
1

ACCEPTED MANUSCRIPT
Abstract
A novel Ni3O-based MOF, {[Ni3HL(µ3-OH)(H2O)2]·3(H2O)·DMA}n (1), was
constructed based on an organosilicon hexacarboxylic acid linker of
5,5',5''-(methylsilanetriyl)triisophthalic acid (H6L). In this structure, the deprotonated
carboxylate groups assemble with trinuclear metal cluster nodes to give a 6-connected
uninodal net. It possesses open channels and rich metal sites, and displays CO2
adsorption behavior. Further investigations indicate that the compound is catalytically
effective for the cyclic carbonates by cycloaddition of CO2 to epoxides. Besides, the
catalyst could be reused 5 times with no significant loss of catalytic activity and
without structural deterioration.
Keywords: metal cluster; CO2 adsorption; CO2 cycloaddition; catalyst
2

ACCEPTED MANUSCRIPT
1. Introduction
There has been an increasing research interest in CO2 capture, storage and
utilization, due to awareness of a rapid growth in CO2 emission in the atmosphere and
the consequent global warming [1]. Efficient transformation of CO2 into valuable
chemicals in the catalysis is very attractive both academically and industrially,
because CO2 is an abundant C1 building block in organic synthesis and is recognized
to be inexpensive and renewable [2]. The cost-effective procedures have been
developed by forming C-C, C-N, C-O and C-H bonds to convert CO2 into
value-added chemicals [3–6]. However, because CO2 molecules possess
thermodynamic stability and kinetic inertness, efficient chemical fixation of CO2
remains difficult under mild conditions. In order to overcome such barriers, a
relatively high free energy is essential for a reaction. In this area, coupling of CO2 and
epoxide to cyclic carbonates presents one of the most promising methodologies [7-9].
Moreover, the addition of CO2 to epoxides is a 100% atom-efficient reaction with no
by-products. The produced cyclic carbonate is widely used as polar aprotic solvent,
electrolyte, and raw material for polycarbonate [10].
Homogeneous and heterogeneous catalysts are two main classes of catalytic systems
developed for this CO2 transformation. Homogeneous systems are accepted to be
effective, but generally undergo a complicated separation of the catalysts from the
reaction product [11-13]. Several types of heterogeneous catalysts have been applied
to the chemical fixation of CO2 to form cyclic carbonate [14-16]. However, many
catalysts suffer from an inhomogeneous distribution of active sites that reduce product
selectivity [17]. Metal-organic frameworks (MOFs), a class of crystalline porous
solids with infinite networks built from inorganic metal ions/cluster and organic
linkers [18-21], have been demonstrated to be promising heterogeneous catalysts in
various reactions [22-24]. On basis of the relationship between the function of MOFs
and modular nature at the molecular level, decorating the pore environment with rich
Lewis acidic sites can endow them with desirable catalytic activity [25]. Focusing on
the above considerations, a metal cluster-based MOF could be an ideal candidate for
CO2 conversion with epoxides in virtue of the more active sites compared with the
3

ACCEPTED MANUSCRIPT
single metal center at the node.
In this work, a novel porous MOF of {[Ni3HL(µ3-OH)(H2O)2]·3(H2O)·DMA}n 1
(DMA = N,N’-dimethylacetamide) was obtained under solvothermal condition.
Compound 1 is built from inorganic Ni3-O cluster and organic steric linker of
5,5',5''-(methylsilanetriyl)triisophthalic acid (H6L). With open channels and rich metal
sites, the compound exhibits CO2 capture and conversion under mild reaction
condition. Its catalytic activity is greatly superior to most MOF-based catalysts, and
its structure as heterogeneous catalyst can be recycled at least five runs without a
significant compromise of catalytic activity.
2. Experimental section
2.1 Materials and methods
All materials are commercially available and were used without further purification
except for 5,5',5''-(methylsilanetriyl)triisophthalic acid (H6L), which was synthesized
in our laboratory.
Scheme 1 The synthesis of 5,5',5''-(methylsilanetriyl)triisophthalic acid.
2.2 Synthesis of compound 1
First, a mixture of Ni(NO3)2·6H2O (29 mg, 0.1 mmol) and H6L(27 mg, 0.05 mmol )
were dissolved in 6 mL of a mixed solvent (DMA:H2O = 1:5 (V/V)), and were
transferred into a 20 mL tube, which was sealed with a rubber septum and placed in a
screw-capped vial. Then the resulting mixture was kept in an oven at 150 °C for 3
days under autogenous pressure. After cooled to room temperature, green block
crystals were separated by centrifugation. After washing several times with DMA, the
crystals were dried at ambient temperature. Yield: 36 mg (~40% based on Ni2+ ions).
Elemental analysis (%) Calcd for compound 1: C, 38.54; H, 3.68; N, 1.55; Found: C,
4

ACCEPTED MANUSCRIPT
38.28; H, 3.86; N, 1.33. IR (KBr, cm−1, Figure S5): 3360 (vs), 1604 (s), 1539 (s),
1401 (s), 1345 (vs), 1259 (w), 1193(w), 1121 (w), 1019 (w), 880 (w), 838 (w), 778
(w), 728 (w).
2.3 Single-crystal X-ray crystallography
Single-crystal X-ray diffraction (SXRD) data of the title compound were collected
on a Bruker diffractometer using Cu Ka radiation (λ = 1.54178 Å) at 293 K. Data
processing was accomplished with the SAINT processing program [26]. The structure
was solved by the direct methods and refined by full-matrix least-squares fitting on F2
using the SHELXTL crystallographic software package [27]. Non-hydrogen atoms
were refined with anisotropic displacement parameters during the final cycles. All
hydrogen atoms of the organic molecule were placed by geometrical considerations
and were added to the structure factor calculation. The guest molecules were
disordered and could not be modelled properly, the diffused electron densities
resulting from them were removed by the SQUEEZE routine in PLATONS3 and the
results were appended in the CIF file. The reported refinements are of the guest-free
structures using the *.hkp files produced using the SQUEEZE routine.
Crystallographic data for {[Ni3HL(µ3-OH)(H2O)2]·3(H2O)·DMA}n (1893964) has
been deposited with Cambridge Crystallographic Data Centre. Data can be obtained
free of charge upon request at www.ccdc.cam.ac.uk/data_request/cif. Crystal data and
structure refinement is summarized in Table S1.
2.4 Characterization
Powder X-ray diffraction (PXRD) of compound 1 samples were carried out on a
MiniFlex 600 X-ray powder diffractometer equipped with a CuKα (λ = 1.54 Å) over
2θ range of 5-50o at room temperature. The N2 and CO2 adsorption measurements
5

ACCEPTED MANUSCRIPT
were performed on automatic volumetric adsorption equipment (Quantachrome
Autosorb-iQ). The samples were degassed at 150 oC for 10 hours prior to adsorption.
The thermal stability of the sample was evaluated using a SDT 2960 Simultaneous
DSC-TGA of TA instruments under an air atmosphere; 10 mg of the sample was
o
o
heated at a heating rate of 10 C/min up to 900 C under nitrogen flow. Elemental
analyses for C, H, and N were performed by a VarioEL analyzer. The infrared (IR)
spectra (diamond) were obtained using a Nicolet 7600 FT-IR spectrometer within the
1
4000-500 cm-1 region. H NMR spectra were recorded in CDCl3 solvent on a Bruker
400 MHz spectrometer. The chemical shift is given in dimensionless δ values and is
1
referenced relative to TMS in H spectroscopy. Inductively coupled plasma (ICP)
analyses were carried out on a Perkin-Elmer Optima 3300DV spectrometer.
For the ICP procedure, firstly, the filter liquor after catalytic reaction is incinerated
at about 500 degrees in the ceramic crucible; secondly, the alkali is dissolved; thirdly,
the acid is neutralized; finally, the solution is added to the instrument for analysis.
2.5 Cycloaddition of CO2 to epoxides
Prior to gas adsorption and catalytic experiments, the crystals were immersed in
methanol, and then decanted and replenished 3 times for 3 days to remove the
non-volatile DMA solvates. The resulting methanol-exchanged samples of compound
1 were transferred as suspension to a Buchner funnel, and the solvents were decanted.
Then the samples were degassed under a dynamic vacuum at150 °C for 10 hours. The
activated materials were stored in a desiccator under vacuum.
In a typical catalytic reaction, the epoxides (20 mmol, 1850 mg for epichlorohydrin,
2400 mg for styrene oxide, 1420 mg for glycidol), activated compound 1 (0.005 mmol,
4 mg), and co-catalyst of tetrabutylammonium bromide (TBAB, 0.3 mmol) were
mixed in a 20 mL autoclave reactor under solvent free environment. The reaction was
purged with 1 MPa CO2 under a constant pressure for 5 min to allow the system to
equilibrate. The vessel was connected to a CO2 source via a one-way to keep the
pressure at the constant level. After that, the reactor was placed in an oil bath, and the
temperature was increased to 373 K with frequent stirring under the pressurized
6

ACCEPTED MANUSCRIPT
conditions for a period of 3-12h. When the reaction was finished, the reactor was
placed in an ice bath to be quickly cooled down. At the same time, the pressure was
released slowly. A small aliquot of the supernatant reaction mixtures were dissolved in
0.6 mL of CDCl3. The obtained solution was filtered by a syringe filter (PTFE) to be
analyzed by 1H NMR for calculating the conversion of the epoxide.
For the recycle experiment, the catalyst was separated by centrifugation after the
1
reaction, and the supernatant was collected and analyzed by H NMR. The residual
solid was washed with dichloromethane and centrifuged three times and dried at 100
◦C for 2 h under vacuum. The recovered catalyst was reused in the following reactions
under the same conditions as the first run.
The conversion was calculated from 1H NMR according to the following equation.
The TON ( turnover number) and TOF (turnover frequency) were calculated
according to the following equations.
n(epoxide)
TON =
n(catalyst)
n(epoxide)
TOF =
n(catalyst)× h
3. Results and discussion
3.1 Structure characterization
Single crystal X-ray diffraction analysis revealed that compound 1 was crystalized in
the space group monoclinic C2/c. Its formula was determined to be
{[Ni3HL(µ3-OH)(H2O)2]·3(H2O)·DMA}n by single-crystal X-ray diffraction, charge
balance consideration, thermogravimetric analysis (TGA) and elemental analysis. The
asymmetric unit of the host framework contains three crystallographically
independent Ni2+ ions, one µ3-OH-, one HL5- ligand and two coordinated water
7

ACCEPTED MANUSCRIPT
molecules. Ni1, Ni2 and Ni3 are bridged by six carboxyl groups into a trinuclear unit
as secondary building unit (SBU), which is constructed from two [NiO6] octahedron
and one [NiO4] tetrahedron fused at one shared OH- corner (Fig. S1a). The trinuclear
clusters are further linked by carboxylate groups to afford a porous 3D framework
(Fig. 1a). Each ligand links ten Ni atoms with six carboxylate arms by four µ2-η1,η1,
one µ1-η1,η0 and one µ1-η1,η1 carboxylate groups. For clarity, the {Ni3} cluster as a
six-coordinated node is here simplified as a wine-red octahedron; while the
six-connected ligand is shown as an outstretched linker with three green triangles (Fig.
1b). The assembly of abstracted geometric shape is presented in Fig. 1b. According to
topological analysis, it is a 6-coordinated uninodal net with a point symbol of {411·64}
(Fig. S2) [28]. There are four types of channels (Fig. S3), the apertures of which are
about 7.9× 8.1 Å2, 8.1 × 6.2 Å2 and 7.8 × 3.9 Å2 and 7.3 × 7.3 Å2 along the b-axis
(atom to atom distance). The solvent-accessible volume is approximately 3264 Å3 per
unit cell volume of 7875.6 Å3, with a pore volume ratio of 41.5% calculated by the
PLATON program [29]. The porosity of compound 1 was confirmed by N2
adsorption-desorption measurements at 77K, and the result isotherm featuring type I
yielded a Brunauer-Emmett-Teller (BET) surface area of 743.5 m2 g−1.
Fig.1. A view of the 3D architecture of the framework 1 in ball-stick model (a) , and the assembly
of abstracted geometric shapes (b), wherein the {Ni3} clusters are shown as octahedron, and the
benzene rings are simplified as triangles.
8

ACCEPTED MANUSCRIPT
3.2 Thermogravimetric analysis (TGA ) and powder X-ray diffraction analysis
(PXRD)
The thermal stability of the compound was evaluated by thermogravimetric
analysis (TGA) under N2 atmosphere. The TGA curve revealed that a weight loss of
19.53% can be observed from room temperature (RT) to 305 °C, corresponding to the
loss of free water and DMA molecules, as well as the coordinated water molecules
(calcd: 19.61%). With the temperature increasing, compound 1 starts to decompose.
The bulk phase of compound 1 was confirmed by powder X-ray diffraction (PXRD)
analyses. The diffraction patterns of fresh samples are in good agreement with the
simulated ones, indicating that compound 1 is pure phase. Besides, the activated and
catalyzed samples of 1 were also showed diffraction patterns similar to that of the
pristine sample (Fig. S4), indicating structural permanent microporosity and integrity.
3.3 Catalytic properties
It is well known that Lewis acid sites are able to catalyze the cycloaddition of CO2
and epoxides to produce cyclic carbonates. Therefore, polynuclear metal sites, good
thermal stability and permanent porosity of 1 inspired us to explore its utilization as
heterogeneous catalyst for the synthesis of cyclic carbonates by the coordinatively
unsaturated Ni2+ ions as Lewis acidic sites. The affinity toward CO2 for compound 1
was firstly evaluated by CO2 sorption measurement (Fig. S8), which showed that the
CO2 uptake was up to 34.6 cm3 g-1 at 273K and 1.0 atm.
The initial research was focused on the reaction of glycidol with CO2 in the
presence of n-Bu4NBr (TBAB, 1.5 mol%) as co-catalyst under an optimum condition
o
of 100 C and 1 MPa, which is based on previous report for reference [30]. The
typical reaction was performed using 20 mmol of epoxides and 0.005 mmol of
compound 1, the load of catalyst was 0.025 mol% ration based on {Ni3} cluster. It
was found that corresponding cyclic carbonates were yielded in an approximate
quantitation within 3 hours, with turnover frequency (TOF) value of 1333 h-1 per
{Ni3} cluster. Such an encouraging result inspired us to investigate other epoxides.
When epichlorohydrin was employed, the reaction yield catalyzed by 1 was 95% for 3
hours, and >99% for 6 hours. A small activity decrease may be associated with
9

ACCEPTED MANUSCRIPT
different electron-withdrawing substituents [31]. During the ring opening of the
epoxide, electron-withdrawing substituents facilitate nucleophilic attack [31]. The
electronegativity of oxygen is bigger than chlorine, as a consequence, the yield
reduced a little when hydroxyl group in glycidol was substituted by chlorine group.
Above catalytic results indicate that compound 1 possesses excellent catalytic
performances for small-sized epoxide substrate. To verify the catalytic generality of
compound 1, a larger epoxide substrate of styrene oxide (SO) was introduced. A
significant change in the conversions were observed, and the yields of corresponding
cyclic carbonate were ~39% in 3h, ~65%in 6h, and ~90% in 12 h under the same
reaction conditions. This phenomenon may be mainly attributed to size effect, because
the number of substrate molecule per unit porosity volume would reduce as the its
size increase. However, the catalytic efficiency of compound 1 in any case is still
more higher than most documented MOFs in the cycloaddition of CO2 to epoxides, as
shown in Table 1.
Table 1. Comparisons with the best MOF catalysts documented in the
cycloaddition reaction of CO2 and epoxides.
Catalyst
Substrate
TON
20
t (h)
12
3
TOF (h-1)
Ref.
32
{Eu(BTB)(phen)} b
2
4000
593
1333
99
This work
33
1
Gea-MOF-1a
6
O
Cl
4000
2000
6
667
167
This work
30
1
Ni-TCPE-1c
1
12
3600
12
300
This work
The results in this work were obtained at 373 k and under 1 MPa CO2
pressure. Reaction conditions in other works: a, 393 K, 2.0 MPa; b, 303 K,
0.1 MPa; c, 373K, 1 MPa. TON: turnover number. The conversions were
determined by 1H NMR analysis.
10

ACCEPTED MANUSCRIPT
Besides, reusable experiments were carried out to verify the heterogeneous nature
of compound 1. Herein, the glycidol was employed as the substrate in view of high
conversion and easy segregation of its cycloaddition. Since a complete conversion for
glycidol took 3 hours, the catalyst was isolated and reused every 3 hours, and the
1
conversions were determined by H NMR analysis. It was found that the yields did
not obviously decrease even after five successive runs (Fig. S9). In addition, it is
worth noting that the loading is very small. An unavoidable loss of catalyst would
cause an inaccurate decrease of yield. After the fifth reaction, inductively coupled
plasma (ICP) analysis was performed on the mixture filtrate. There was no Ni
leaching, further proving that the reaction catalyzed by compound 1 was indeed
heterogeneous. Besides, PXRD measurements were used to confirm the structural
integrity of the recovered catalyst (Fig. S4).
A reasonable mechanism was proposed for the cyclic addition of CO2 and epoxides
in the presence of compound 1 (Scheme 2), similar to that of previous reports [30, 33].
o
After pretreatment at 150 C, the coordinated H2O molecules were removed to form
unsaturated coordinative Ni atoms, then the {Ni3} clusters could act as Lewis acid.
Firstly, the CO2 and substrate molecules enter channels and are adsorbed on the Lewis
acid sites of activated 1, and the unsaturated coordinative Ni synchronously binds to
the oxygen atom of epoxide, making it more susceptible for ring-opening. Secondly,
the nucleophilic reagent Br− of TBAB attacks the activated carbon atom of epoxide,
leading to the ring open and producing the metal/heteroatom alkoxide intermediates
(step 1). Finally, the anion intermediate reacts with CO2, and the ring-closure forms
the final cyclic carbonate. At the same time, the Br- and the catalyst are regenerated,
respectively.
11

ACCEPTED MANUSCRIPT
O
O
R
O
Br-
R
O
Br
R
O
O
O
Br
O
R
O
C
O
Scheme 2 The proposed mechanism of the cyclic addition of CO2 and epoxide
catalyzed by activated 1 (dark rectangle: channel; green sphere: {Ni3} cluster).
4. Conclusions
In summary, a new and highly efficient catalyst based on {Ni3} cluster has been
developed. The compound catalyzes the coupling reaction of epoxides with CO2 at
373K and under 1 MPa CO2 pressure to produce cyclic carbonates with high yields.
Intensive investigation including cycle experiments and catalyst filtration test confirm
that activated 1 operates as a heterogeneous catalyst. Moreover, its catalytic activity
remains high after several reuses.
Acknowledgments. This work was financially supported by the Doctoral Scientific
Research Foundation of Inner Mongolia University for Nationalities (BS462), the
Open Projects Founded by Inner Mongolia Key Lab of Carbon Nanomaterials
(MDK2018040), the Open Projects Founded by Inner Mongolia Key Laboratory for
the Natural Products Chemistry and Functional Molecular Synthesis (MDK2017053,
MDK2017056), and the Scientific Research Program of Inner Mongolia University
for Nationalities (NMDGP1703 and NMDYB1728).
12

ACCEPTED MANUSCRIPT
References
[1] Q. Wang, J. Luo, Z. Zhong, A. Borgna, Energy Environ. Sci. 4 (2011) 42–55.
[2] J. Ma, N. Sun, X. Zhang, N. Zhao, F. Xiao, W. Wei, Y. Sun, Catal. Today 148
(2009) 221–231.
[3] I. Omae, Coord. Chem. Rev., 256 (2012) 1384–1405.
[4] M. North, R. Pasquale and C. Young, Green Chem., 12 ( 2010) 1514–1539.
[5] Y. N. Li, R. Ma, L. N. He and Z.-F. Diao, Catal. Sci. Technol., 4 (2014)
1498–1512.
[6] B. Yu and L. N. He, ChemSusChem, 8 (2015) 52–62.
[7] M. Ding and H.-L. Jiang, ACS Catal., 8 (2018) 3194-3201.
[8] M. Ding, S. Chen, X.-Q. Liu, L.-B. Sun, J. Lu and H.-L. Jiang, ChemSusChem, 10
(2017) 1898-1903.
[9] W. Jiang, J. Yang, Y.-Y. Liu, S.-Y. Song and J.-F. Ma, Chem. Eur. J., 22 (2016)
16991-16997.
[10] B. Schäffner, F. Schäffner, S.P. Verevkin, A. Börner, Chem. Rev. 110 (2010)
4554.
[11] B. Chatelet, L. Joucla, J. P. Dutasta, A. Martinez, K. C. Szeto and V. Dufaud, J.
Am. Chem. Soc., 135 (2013) 5348-5351.
[12] B. H. Xu, J. Q. Wang, J. Sun, Y. Huang, J. P. Zhang, X. P. Zhang and S. J. Zhang,
Green Chem., 17 (2015) 108-122.
[13] X.-B. Lu and D. J. Darensbourg, Chem. Soc. Rev., 41 (2012) 1462-1484.
[14] M.-P. Liu, Y.-P. Luo, L. Xu, L. Sun and H.-B. Du, Dalton Trans., 45 (2016)
2369-2373.
[15] M. E. Wilhelm, M. H. Anthofer, M. Cokoja, I. I. E. Markovits,W. A. Herrmann
and F. E. Kuhn, ChemSusChem, 7 (2014) 1357-1360.
[16] Q. Sun, N. Wang, Q. Bing, R. Si, J. Liu, R. Bai, P. Zhang, M. Jia, and J. Yu,
Chem, 3 (2017) 477-493.
[17] M. North, R. Pasquale and C. Young, Green Chem., 12 [2010] 1514-1539.
[18] H.-C. Zhou, J. R. Long and O. M. Yaghi, Chem. Rev., 112 (2012) 673-674.
[19] M. Ding and H.-L. Jiang, ACS Catal., 8 (2018) 3194-3201.
13

ACCEPTED MANUSCRIPT
[20] J. Zhao, W.-W. Dong, Y.-P. Wu, Y.-N.Wang, C. Wang, D.-S. Li and Q.-C.
Zhang, Mater. Chem. A, 3 (2015) 6962-6969.
[21] (a) W.-W. Xiong, J. Miao, K. Ye, Y. Wang, B. Liu, Q. Zhang, Angew Chem Int.
Ed., 54 (2015) 546-550; (b) W.-W. Xiong, Q. Chun, Angew Chem. Int. Ed., 54 (2015)
11616-11623; (c) P. Li, F.-F. Cheng, W.-W. Xiong, and Q. Chun, Inorg. Chem. Front.,
1 (2014) 292-301; (d) W.-W. Xiong, E. U. Athresh, Y. T. Ng, J. Ding, T. Wu, and Q.
Chun, J. Am. Chem. Soc., 135 (2013) 1256-1259; (e) W.-W. Xiong, P.-Z. Li, T.-H.
Zhou, A. L. Y. Tok, R. Xu, Y. Zhao, and Q. Zhang, Inorg. Chem., , 52 (2013)
4148-4150; (f) D.-D., Yang, Y. Song, B. Zhang, N.-N. Shen, G.-L. Xu, W.-W. Xiong,
and X.-Y. Huang, Cryst. Growth Des., 18 (2018) 3255−3262; (g) W.-W. Xiong, G.
Zhang, and Q. Zhang, Inorg. Chem. Front. , 5 (2018) 2693-2708.
[22] H.-X. Zhang, M. Liu, T. Wen and J. Zhang, Coord. Chem. Rev., 307 (2016)
255-266.
[23] K. J. Lee, J. H. Lee, S. Jeoung and H. R. Moon, Acc. Chem. Res., 50 (2017)
2684-2692.
[24] T. Zhang and W. Lin, Chem. Soc. Rev., 43 (2014) 5982-5993.
[25] M. H. Beyzavi, C. J. Stephenson, Y. Liu, O. Karagiaridi, J. T. Hupp and O. K.
Farha, Front. in Energy Res., 2 (2015) 63.
[26] SMART and SAINT software package, Siemens Analytical X-ray Instruments
Inc., Madison, WI, 1996.
[27] (a) O.V. Dolomanov, L.J. Bourhis, R.J. Gildea, J. A. K. Howard and H.
Puschmann, J. Appl. Cryst. 42 (2009) 339-341; (b) G. M. Sheldrick, ActaCryst. A, 64
(2008) 112-122; (c) G. M. Sheldrick, ActaCryst. C, 71 (2015) 3-8.
[28] V. A. Blatov, Struct. Chem., 23 (2012) 955-963, TOPOS software is available for
download at http://www.topos.samsu.ru.
[29] A. L. Spek, J. Appl. Crystallogr., 36 (2003) 7-13.
[30] Z. Zhou, C. He, J. Xiu, L. Yang and C. Duan, J. Am. Chem. Soc. 137 (2015)
15066.
[31] A. Kilic, A. A. Palali, M. Durgun, Z. Tasci, M. Ulusoy, Spectrochim. Acta Part A.
113 (2013) 432-438.
14

ACCEPTED MANUSCRIPT
[32] H. Xu, B. Zhai, C.-S. Cao, and B. Zhao, Inorg. Chem., 55 (2016) 9671-9676.
[33] V. Guillerm, Ł. J. Weseliński, Y. Belmabkhout, A. J. Cairns, V. D’Elia, Ł. Wojtas,
K. Adil and M. Eddaoudi, Nature Chem. 6 (2014) 673-680.
15

ACCEPTED MANUSCRIPT
► A {Ni3}-cluster based network has been successfully developed as an efficient
catalyst for CO2 cycloaddition.
► Its catalytic activity is superior to most documented MOF-based catalysts.
► The heterogeneous catalyst can be recycled at least five runs without a significant
compromise of catalytic activity.